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WO2016005042A1 - Procédé de récupération d'acide chlorhydrique contenu dans des solutions de chlorure métallique à teneur élevée en chlorure de fer - Google Patents

Procédé de récupération d'acide chlorhydrique contenu dans des solutions de chlorure métallique à teneur élevée en chlorure de fer Download PDF

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Publication number
WO2016005042A1
WO2016005042A1 PCT/EP2015/001364 EP2015001364W WO2016005042A1 WO 2016005042 A1 WO2016005042 A1 WO 2016005042A1 EP 2015001364 W EP2015001364 W EP 2015001364W WO 2016005042 A1 WO2016005042 A1 WO 2016005042A1
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WO
WIPO (PCT)
Prior art keywords
hydrochloric acid
hcl
iron
metal chloride
pyrohydrolysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2015/001364
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German (de)
English (en)
Inventor
Oliver Gnotke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kronos International Inc
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Kronos International Inc
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Filing date
Publication date
Application filed by Kronos International Inc filed Critical Kronos International Inc
Publication of WO2016005042A1 publication Critical patent/WO2016005042A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • C01B7/0706—Purification ; Separation of hydrogen chloride
    • C01B7/0731—Purification ; Separation of hydrogen chloride by extraction
    • C01B7/0737—Purification ; Separation of hydrogen chloride by extraction hydrogen chloride being extracted
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/035—Preparation of hydrogen chloride from chlorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors

Definitions

  • the invention is directed to a process for the recovery of hydrochloric acid from concentrated metal chloride solutions which have a high proportion of iron chloride and are obtained in particular in the acid leaching of ores or in the pickling of rolled steel products.
  • Acid recovery is an essential process feature in all processes involving acid leaching and acid pickling, respectively, for economic reasons.
  • hydrochloric acid which is used for example for pickling steel before electroplating, from the pickling solutions are numerous
  • pyrohydrolysis which is carried out in a spray roaster or in a fluidized bed roaster at temperatures around 800 ° C.
  • the metal chlorides are converted as quickly and completely as possible into the oxides (such as Fe 2 O 3 ) and HCl (Baerhold, FH & Lebl, A. "Recycling of acids via pyrohydrolysis: fundamentals and applications", REWAS'99 Global Symposium on recycling , waste treatment and clean technology, Vol. II, (1999) p. 1297-1307).
  • the plants required for the processing of steel pickling are usually much smaller than those for the treatment of ore leach solutions.
  • the largest plant for pickling solutions processes 18 m 3 / h of ferric chloride solution.
  • the size of the pyrohydrolysis apparatuses is limited due to the high temperatures and thus the very large gas flow rate, so that one would have to work with ore leaching with a variety of parallel acid regeneration systems.
  • WO 1993/016000 A1 discloses a process for the recovery of hydrochloric acid from iron (II) chloride-containing leach solutions, which prior to pyrohydrolysis a
  • Preconcentration and then pelletization of the chloride solution provides.
  • the preconcentration takes place in a Venturi nozzle or spray system and through
  • the metal chloride concentrate is pelleted and dried at temperatures of 130 to 150 ° C.
  • the dried pellets are subsequently thermally split in the fluidized bed roaster (pyrohydrolysis).
  • the HCI-containing offgas is passed over a HCI absorption column, and an azeotropic hydrochloric acid (18 to 20 wt .-%) is recovered.
  • This process has the advantage that a large part of the evaporation of water takes place at low temperatures (drying temperature 130-150 ° C.) and thus in a plant a multiple (up to four times) of the throughput compared to a single-stage fluidized bed can be achieved. Since in the acid leaching of iron-containing ores (ilmenite) significantly larger amounts of metal chloride solutions than steel pickling, it is desirable to work with the highest possible acid concentration, since this in the pyrohydrolysis to
  • FeCl 3 has a higher solubility than FeCl 2 , it evaporates at the temperatures prevailing in the fluidized bed roaster during pyrohydrolysis and then hydrolyzes in the gas phase. It forms dust-fine iron oxide particles, which in turn can not be separated from the HCI gas stream with the usual aggregates (see: Baerhold & Lebl (1999) page 1298 below).
  • the invention is based on the object, a method for the preparation of
  • the object is achieved by a process for the recovery of hydrochloric acid from a metal chloride solution, with a concentration of at least 20 wt .-%, wherein the
  • step b) pyrohydrolysis of the resulting in step a) granules in a reactor at temperatures above 550 ° C, preferably above 800 ° C, wherein HCl-containing gas is formed, c) recovery of hydrochloric acid from the in the process steps a) and / or b ) resulting HCI-containing gases.
  • FIG 1 Schematic process flow diagram: Variant A.
  • FIG. 2 Schematic process flow diagram: variant B
  • Figure 3 Scanning electron micrograph of a cut pellet from the spray granulation according to Example.
  • the metal chloride solution used according to the invention has a metal chloride concentration of at least 20% by weight, preferably at least 30% by weight and in particular from 40 to 60% by weight, the proportion of iron chloride being more than 50% by weight and preferably more than 70% Wt .-% is. Furthermore, the Fe 3+ / Fe 2+ ratio is at least 0.2.
  • the process according to the invention is based on the process according to WO 1993/016000 A1, but part of the iron chloride is present as FeCl 3 and the pelletization step is carried out at a higher temperature of 150 to 300 ° C. so that at least part of the iron chloride already hydrolyzes and converted to iron oxide and HCl.
  • the metal chloride solution is first preconcentrated as in the known method according to WO 1993/016000 A1.
  • a significantly higher Fe concentration than the usual 120 g / l Fe can be set without it
  • Crystallization occurs in the Venturi nozzle system. If a high proportion up to the total amount of dissolved iron trivalent - for example due to an oxidative pretreatment of the ilmenite before the acid leaching - the metal chloride solution can be preconcentrated to up to 60% by weight, without forming solid iron chloride.
  • the metal chloride solution optionally a preconcentration was subjected to spray granulation at temperatures of 150 to 300 ° C, preferably 150 to 250 ° C, wherein the solution is injected via a plurality of spray nozzles in a fluidized bed (step a).
  • the FeCl 3 content largely hydrolyzes and the FeCl 2 content partially hydrolyzes to form iron oxide according to the following reaction scheme:
  • the largest possible proportion of the iron chloride is hydrolyzed.
  • the spray granule fluidized bed is preferably heated via a hot gas generator.
  • the supply air temperature should be between 300 ° C and 1000 ° C, preferably> 600 ° C. It forms a ferric chloride-containing iron oxide granules (pellets) of about 1 to 5 mm in size.
  • the addition of granulation seeds in the form of recycled cyclone dust or other solids is advantageous.
  • the combustion in the hot gas generator should be done with as little air excess as possible.
  • the avoidance of free oxygen in the exhaust gas of the spray granulation is used for.
  • Minimizing the Deacon reaction formation of chlorine, which can occur at low temperatures.
  • the process according to the invention thus differs from the process according to WO 1993/016000 A1, in which a FeCl 2 solution is preconcentrated and pelleted without a hydrolysis reaction taking place. The hydrolysis and thus the formation of iron oxide from iron chloride according to WO 1993/016000 A1 only in the subsequent
  • the pellets are conveyed through a suitable transport apparatus into the pyrohydrolysis reactor (step b).
  • the pyrohydrolysis reactor is preferably a fluidized bed reactor which is operated at a temperature above 550 ° C, preferably above 800 ° C and especially at about 850 ° C, the material lasting several hours
  • the produced granular metal oxide essentially contains iron oxide.
  • the gas streams leaving the spray granule fluidized bed (step a) and the pyrohydrolysis fluidized bed (step b) contain the hydrochloric acid to be recovered.
  • the HCl The content of the gas flow exiting the spray granulation fluidized bed depends on the total iron chloride content and the Fe 3+ Fe 2+ ratio in the
  • Spray granulation fluidized bed entering metal chloride solution The exiting gas streams are passed into HCI absorption columns of the prior art.
  • the exhaust gases of the spray granulation and the pyrohydrolysis are each passed into a packed column, wherein via a
  • Recirculation line by means of pumping additional wash liquid can be returned to the top of the column to the necessary wetting of the packed body
  • a heat exchanger can be integrated to set advantageous isothermal conditions. Since the absorption of HCl is exothermic, the solubility of HCl in the washing liquid decreases with increasing temperature, higher hydrochloric acid concentrations can be achieved with cooling than without.
  • the reaction gases are usually sucked off via blowers which each sit above the column heads. As a result, advantageously also a negative pressure in the system, which prevents harmful HCI-containing gases from entering the environment.
  • superazeotropic hydrochloric acid can be recovered with a concentration of> 20% by weight, preferably> 25% by weight and in particular> 30% by weight. From the vapor-liquid balance can be deduced that for a
  • the washing liquid used is preferably the effluent of the HCI absorption column of the pyrohydrolysis (see Fig. 1: Process variant A). If the FeCl 3 content of the input solution is lower, the gas stream of the pyrohydrolysis is the HCI-richer gas stream and this is passed into an absorption column to generate superazeotropic hydrochloric acid. The effluent of the HCl absorption column of the spray granulation is then preferably used as the scrubbing liquid (see Fig. 2: Process variant B).
  • the exhaust gas streams may optionally be subjected to another gas scrubbing to comply with statutory limits.
  • the method according to the invention has the following advantages over the prior art:
  • Solutions are recovered, whereby the acid loops necessary in acid tanning and the necessary evaporation of water can be kept small. Solutions with a high FeCl 3 content can be processed.
  • the resulting metal oxide is granular (> about 500 ⁇ ), contains essentially iron oxide and has a low residual chloride content, making it good as a raw material for the
  • Ilmeniterz from Norway was without prior reduction with 25% hydrochloric acid under. Leaching conditions. The residue was filtered off.
  • Mn, Cr, V, Al and Ca chlorides were each ⁇ 1% by weight.
  • the bed temperature was controlled by the fuel supply to 160 ° C.
  • the resulting pellets were withdrawn continuously.
  • the resulting exhaust gas was washed in a column.
  • the resulting pellets had a diameter of 1 to
  • the free moisture was 3 to 4 wt .-%.
  • the exhaust gas of the spray granulation fluidized bed had the following composition: H 2 0 38 vol.%,
  • pellets were treated in a pyrohydrolysis fluidized bed.
  • Fluidized bed had a diameter of 10 cm, was externally heated and through
  • Fuel addition preheated directly in the fluidized bed to 950 ° C. Then about 3 kg of the pellets were metered into the fluidized bed over a period of about 3 hours. The temperature was kept constant at 950 ° C by further addition of fuel. After this time, the addition and heating was stopped.
  • the treated pellets contained 90% by weight of Fe 2 O 3 and 5.7% by weight of MgO. As further constituents, Mn, Cr, V, Al and Ca oxides each had ⁇ 1% by weight. The proportion of total chlorides was less than 0.5 wt .-%.
  • the average diameter of the pellets (d 50 mass-related) was about 800 ⁇ , the bulk density at 2300 kg / m 3 .
  • the exhaust gas of the pyrohydrolysis fluidized bed was first quenched by spraying water to about 100 ° C and then collected in a column into which water was added. Before and after the quenching, the exhaust gas of the pyrohydrolysis had the following composition:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de récupération d'acide chlorhydrique contenu dans des solutions de chlorure métallique concentrées (concentration ≥20 % en poids), qui présentent une teneur en chlorure de fer supérieure à 50% en poids calculée en tant que Fe, le rapport Fe3+/Fe2+ étant d'au moins 0,2. Le procédé selon l'invention comprend les étapes suivantes : a) granulation par pulvérisation de la solution de chlorure métallique à des températures comprises entre 150 et 300°C, de préférence entre 150 et 250°C. au moins une partie du chlorure de fer étant convertie en oxyde de fer par hydrolyse et un granulat ainsi que du gaz contenant HCl étant obtenus, b) pyrohydrolyse du granulat obtenu à l'étape a) dans un réacteur à des températures supérieures à 550°C, de préférence supérieures à 800°C, ce qui donne lieu à la formation de gaz contenant HCl, c) récupération d'acide chloridrique contenu dans les gaz contenant HCl produits aux étapes a) et/ou b). Le procédé selon l'invention se caractérise en ce qu'il permet de traiter des solutions à teneur élevée en FeCI3 et en ce qu'une part importante de la vaporisation de l'eau s'effectue à de basses températures et qu'ainsi de hauts rendements peuvent être atteints dans une installation.
PCT/EP2015/001364 2014-07-08 2015-07-03 Procédé de récupération d'acide chlorhydrique contenu dans des solutions de chlorure métallique à teneur élevée en chlorure de fer Ceased WO2016005042A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14002335.9A EP2966035A1 (fr) 2014-07-08 2014-07-08 Procédé de récupération d'acide chlorhydrique à partir de solutions de carbonate de métal à teneur élevée en chlorure ferrique
EP14002335.9 2014-07-08

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WO2016005042A1 true WO2016005042A1 (fr) 2016-01-14

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US (1) US20160137498A1 (fr)
EP (1) EP2966035A1 (fr)
WO (1) WO2016005042A1 (fr)

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MX2019004545A (es) 2016-10-21 2019-11-12 Nantenergy Inc Electrodo de combustible corrugado.
CN106943847B (zh) * 2017-04-20 2023-08-15 成都瑞柯林工程技术有限公司 从酸洗废酸再生系统中回收微细氧化铁粉的装置
CN107161951B (zh) * 2017-07-07 2019-04-19 天津市职业大学 资源化处理含铁工业废盐酸的方法
US11611115B2 (en) 2017-12-29 2023-03-21 Form Energy, Inc. Long life sealed alkaline secondary batteries
CA3105128A1 (fr) 2018-07-27 2020-01-30 Form Energy, Inc. Electrodes negatives pour cellules electrochimiques
US12294086B2 (en) 2019-07-26 2025-05-06 Form Energy, Inc. Low cost metal electrodes
RU2752352C1 (ru) * 2020-09-16 2021-07-26 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Способ переработки отходов растворов хлоридов железа
US20230339770A1 (en) * 2022-04-25 2023-10-26 Form Energy, Inc. High purity iron-bearing materials and systems and methods of production thereof

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WO1993016000A1 (fr) * 1992-02-12 1993-08-19 Austpac Gold N.L. Regeneration d'acide
US20090095132A1 (en) * 2005-06-15 2009-04-16 John David Winter Processing of metal chloride solutions and method and apparatus for producing direct reduced iron
EP2310323A1 (fr) * 2008-06-19 2011-04-20 SMS Siemag Aktiengesellschaft Procédé de traitement permettant de récupérer de l'oxyde de fer et de l'acide hydrochlorique

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US5589097A (en) * 1993-12-24 1996-12-31 Tdk Corporation Method for preparing magnetite magnetic powder
JP4404991B2 (ja) * 1999-06-01 2010-01-27 水澤化学工業株式会社 活性白土定形粒子、その製造方法及びその用途
WO2008034212A1 (fr) * 2006-09-21 2008-03-27 Qit-Fer & Titane Inc. Procédé électrochimique pour la récupération de valeurs de fer métallique et de chlore à partir de déchets de chlorures métalliques riches en fer

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
WO1993016000A1 (fr) * 1992-02-12 1993-08-19 Austpac Gold N.L. Regeneration d'acide
EP0625957B1 (fr) * 1992-02-12 1998-09-02 Austpac Gold N.L. Regeneration d'acide
US20090095132A1 (en) * 2005-06-15 2009-04-16 John David Winter Processing of metal chloride solutions and method and apparatus for producing direct reduced iron
EP2310323A1 (fr) * 2008-06-19 2011-04-20 SMS Siemag Aktiengesellschaft Procédé de traitement permettant de récupérer de l'oxyde de fer et de l'acide hydrochlorique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FRANK H BAERHOLD ET AL: "Recycling of acids via pyrohydrolysis: fundamentals and applications", REWAS '99 : GLOBAL SYMPOSIUM ON RECYCLING, WATER TREATMENT AND CLEAN TECHNOLOGY; PROCEEDINGS OF THE REWAS'99: GLOBAL SYMPOSIUM ON RECYCLING, WASTE TREATMENT AND CLEAN TECHNOLOGY, HELD IN SAN SEBASTIÁN, SPAIN, SEPTEMBER 5-9, 1999; TMS FALL 1999 EXTRAC, vol. 2, 1999, pages 1297 - 1308, XP008172948, ISBN: 978-84-923445-3-6 *

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US20160137498A1 (en) 2016-05-19
EP2966035A1 (fr) 2016-01-13

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